Transmission spectroelectrochemistry

Figure 17.11 Transmission spectroelectrochemistry cell designed for use with room-temperature haloaluminate melts and other moisture-reactive, corrosive liquids, (a) Auxiliary electrode and reference electrode compartments, (b) quartz cuvette containing the RVC-OTE, (c) brass clamping screw, (d) passageway between the separator and OTE compartment, (e) fritted glass separator, (f) A1 plate, (g) lower cell body (Teflon), (h) upper cell body (Teflon). This cell is normally used inside a glove box and is optically accessed with fiber optic waveguides. [From E. H. Ward and C. L. Hussey, Anal. Chem. 59 213 (1987), with permission.]...

Figure 17.1.1 Schematic view of the experimental arrangement for transmission spectroelectrochemistry.

Figure 17.1.2 A Cell for transmission spectroelectrochemistry involving semi-infinite linear diffusion. Light beam passes along vertical axis. [Reprinted from N. Winograd and T. Kuwana, Electroanal. Chem., 7, 1 (1974), by courtesy of Marcel Dekker, Inc.] B Optically transparent thin-layer system front and side views, (a) Point of suction application in changing solutions (b) Teflon tape spacers (c) 1 X 3 in. microscope slides (d) test solution (e) gold minigrid, 1 cm high ...

Figure 3. First cell for transmission spectroelectrochemistry. (Reproduced with permission from Ref. 12. Copyright 1968 Elsevier).

Figure 2.12 (A) Cell for transmission spectroelectrochemistry involving semi-infinite linear dif-...

The technique of transmission spectroelectrochemistry, using an optically transparent electrode (OTE), was first demonstrated in 1964 using o-tolidine, a colourless compound that reversibly undergoes a 2-electron oxidation in acidic solution to form an intensely yellow coloured species (Eqn [1]). This system soon became a standard for testing spectro-electrochemical cells and new techniques. 

Figure 1 Schematic diagram of spectroelectrochemical techniques at an optically transparent electrode (OTE). (A) Transmission spectroelectrochemistry (B) transmission spectro-electrochemistry with an optically transparent thin-layer electrode (OTTLE) cell (C) internal reflection spectroscopy (IRS). Reprinted by courtesy of Marcel Dekker, Inc. from Heineman WR, Hawkridge FM and Blount HN (1984) Spectroelectrochemistry at optically transparent electrodes. II. Electrodes under thin-layer and semi-infinite diffusion conditions and indirect coulometric titrations. In Bard AJ (ed) Electroanalytical Chemistry. A Series of Advances, Vol 13, pp 1-113. New York Marcel-Dekker.

Niu J and Dong S (1996) Transmission spectroelectrochemistry. Reviews in Analytical Chemistry 15 1-171. 

The special properties of OTEs that permit the use of transmission spectro-electrochemical techniques are often at cross purposes with the acquisition of reliable electrochemical data. The desire to have the superior electrical properties of bulk conducting materials, and thereby reliable electrochemical data, together with the power of a coupled optical probe led groups to develop various diffraction and reflection approaches to spectroelectrochemistry. Light diffracted by a laser beam passing parallel to a planar bulk electrode can be used to significantly increase the effective path length and sensitivity in spectroelectrochemistry [66]. 

Figure 17.9 Gas-tight transmission cell for UV-visible spectroelectrochemistry in moderate-melting salts. [From G. Mamantov, V. E. Norvell, and L. Klatt, J. Electrochem. Soc. 727 1768 (1980), with permission.)...

There are several major areas of interfacial phenomena to which infrared spectroscopy has been applied that are not treated extensively in this volume. Most of these areas have established bodies of literature of their own. In many of these areas, the replacement of dispersive spectrometers by FT instruments has resulted in continued improvement in sensitivity, and in the interpretation of phenomena at the molecular level. Among these areas are the characterization of polymer surfaces with ATR (127-129) and diffuse reflectance (130) sampling techniques transmission IR studies of the surfaces of powdered samples with adsorbed gases (131-136) alumina(137.138). silica (139). and catalyst (140) surfaces diffuse reflectance studies of organo- modified mineral and glass fiber surfaces (141-143) metal overlayer enhanced ATR (144) and spectroelectrochemistry (145-149). 

Spectroelectrochemistry, reflection mode — The interaction of electromagnetic radiation with matter (-> spectroscopy) may occur by absorption or scattering when radiation impinges on matter or passes through matter. In the latter case (transmission mode) the radiation before and after passage is evaluated in order to obtain the desired spectrum. In studies of opaque materials or of surfaces interacting with matter inside the (bulk)... 

Electronic Absorption Spectroelectrochemistry. Electronic absorption spectroscopy with UV and visible light is a form of spectroelectrochemistry typically employed as a transmission experiment to investigate changes in absorbance due to a species being oxidized or reduced. Typically the potential is scanned while the absorbance at a particular wavelength is recorded or the potential is stepped while a full spectrum is collected. Spectroelectrochemistry of this type can be used to establish spectroscopic signatures of reduced or oxidized forms of a compound that can be correlated to excited state transient absorbance spectroscopy. 

When spectroelectrochemistry is used as a tool in reaction kinetics, it is important to know accurately the rate of generation of reactive intermediates, that is, the accurate potential of the working electrode. This requirement becomes a particular problem when an OTE is the preferred electrode because of the ohmic drop in the electrode itself and the nonuniform current distributions often encountered. For the OTTLEs in particular, the accurate modeling of the diffusion in the cell also leads to rather complicated mathematical equations [346]. The most profitable way of operation is therefore to use a potential-step procedure where the potential is stepped to a value at which the heterogeneous electron transfer reaction proceeds at the diffusion-controlled rate. In transmission spectroscopy the absorbance, AB(t), of the initial electrode product B, in the absence of chemical follow-up reactions, is given by Eq. (99) [347,348], where b is the extinction coefficient of B. 

These coated glasses can be used as working electrodes [optically transparent electrodes (OTE)] in standard three-electrode arrangements provided that both glass and coating are chemically and electrochemically stable and inert in the used electrolyte solution and the applied range of electrode potentials. The use of a modified infrared spectroscopy transmission cell equipped with quartz windows for UV-Vis spectroelectrochemistry has been described [18]. Platinum layers deposited onto the quartz served as an optically transparent working electrode and an additional platinum layer served as a pseudo-reference electrode. A counter electrode outside the thin layer zone (in one of the tubes used for solution supply) served as a counter... 

A combination of transmission and external reflectance spectroscopy resulting in a cell for bidimensional UV-Vis spectroelectrochemistry has been described [61]. With an optically transparent electrode (OTL), the schematic setup shown in Fig. 5.8 illustrates the different pathways of the light. One beam passes through the electrode and the electrolyte solution in front of it and the second beam passes only through the solution in front of the electrode close to it, guided strictly in parallel to the surface. Thus the former beam carries information pertaining to both the solution and the electrochemical interface (e.g. polymer films or other modifications on the electrode surface), whereas the latter beam carries only information about the solution phase. Proper data treatment enables separation of both parts. Identification of... 

Fig. 5.38. Thin layer cell for NIR spectroelectrochemistry in the transmission mode according to [142, 144]...

Instrumentation. In order to employ local enhancement of infrared absorption by surface plasmon polaritons that cause locally enhanced surface electromagnetic fields, a suitable optical arrangement is needed [295]. Surface enhanced infrared absorption spectroscopy can also be observed in the transmission mode [285, 296]. However, since no application of this approach in spectroelectrochemistry has been reported so far, it is not discussed further. 

In conclusion, UVAds/NIR spectroelectrochemistry in both transmission and reflection mode are extremely useful techniques that yield a wealth of complementary data additional to those obtained in pure electrochemical voltammetric experiments. Especially when based on computer simulation models, this data may be used to unravel the kinetics and thermodynamics of complex electrode processes. 

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